Halogenated cyclic ketones and method for their production



Patented Jan. 26, 1954 HALGGENATED CYCLIC KETONES AND METHOD FOR THEIRPRODUCTION David a. Adelson, Berkeley, Calif., assignor to ShellDevelopment Company, San Francisco, Calif., a corporation of Delaware NoDrawing.

'7 Claims.

This invention relates to the provision of novel compounds formed on thereaction of aliphatical- 1y unsaturated, cyclic ketones withpolyhalogenated organic materials, as well as to the method by whichcompounds are produced. These products are valuable lubricant additives,as disclosed in copending application Serial No. 793,329, filed December22, 1947, now U. S. Patent No. 2,569,122, of which this application is acontinuation-inpart, and many of them are useful for other purposes aswell.

The compounds of this invention are formed by heating one or morealiphatically unsaturated, cyclic ketones with a polyhalogenated organicreactant in the presence of a peroxide catalyst. The resulting productsvary in character from thick, viscous liquids, to resinous solids, andall contain a substantial percentage of halogen.

The cyclic ketone reactant is one wherein the carbonyl carbon atom isembraced in the ring and wherein a double bond of aliphatic characterexists between at least one pair of adjacent carbon atoms which mayeither form a part of said ring or of a group attached thereto.Representative ketones of this class, any one or combination of whichmay be employed for reaction with a polyhalogenated organic compound,are:

Cyclobutenone Cyclopentenone Quinone o-Quinone Isophorone CycloheptenoneCyclohexenone Pulegone Carvone Naphthoquinone Naphthalenone3-vinylcyclohexanone 4-allylcyclohexanone 5-phenyl-3-cyclohexen-1 -one3-methylcycloheXen-2-one 3,3,5-trimethylcyclohexen-2-one However, apreferred class of ketones for use in the present invention comprisesthose wherein an olefinic linkage exists between one or more pairs ofcarbon atoms in the cycle and which contain at least 12 carbon atoms inthe molecule. Representative ketones falling within this preferred classare 3,5,5-triethylcyclohexenone, 3,5,5-triisopropyl-cyclohexenone,dibenzaloyclohexenone, angustione, triquinoyl, and isophorone bottoms(the nature of which will be explained in greater detail below).Generally speaking, higher -ke- Application October 29, 1949, Serial No.124,483

tones of this preferred type may readily be obtained from the catalyticcondensation of acetone either with itself or with some other compoundcondensable therewith to form a higher ketone, examples of such othercondensable compounds being the lower alcohols, as isopropyl, isobutylor isoamyl alcohol. Thus, representative higher ketone may be preparedby condensing acetone in the presence of strong (30 to caustic attemperatures ranging from about to C. and at pressures of from 300 to500 P. S. I., for example. Under favorable circumstances thiscondensation is productive, in the main, of isophorone, though at thesame time various C12 and higher unsaturated ketones are produced whichremain as bottoms after the isophorone and the other lower boilingconstituents have been distilled off. Such bottoms, termed crudeisophorone bottoms, may either be reacted as such with the organicpolyhalogenated compound, or they may first be fractionally distilledinto various components which may then be used in the reaction eitherindividually or in combination. The C12 fraction (C12H1a0) boils withinthe range of approximately 112 to 123 C. (10 mm. Hg), a mixture of C12and C15 (C15H220) ketones boils from about 123 toabout 142 C. (10 mm.Hg), whereas the C15 ketones themselves boil within the range of about140 to C. (10 mm. Hg). A more preferred mixture of unsaturated ketones,termed topped, crude, isophorone bottoms is that which remains in thestill when crude isophorone bottoms are distilled until a still headtemperature of approximately 140 C. (10 mm. Hg) is reached, the residuecomprising, in the main, C12 and higher unsaturated ketones. Isophoronebottoms may also be subjected to hydrolysis with dilute caustic afterwhich they are separated from the acetone and isophorone formed duringthe hydrolysis step. The hydrolyzed bottoms, which can then be filteredor otherwise purified, may be reacted as such with the organic,polyhalogenated material, or they may first be fractionated in themanner described above and then reacted. As was the case with the crudebottoms, a more preferred mixture of ketones is that remaining ondistilling off the components of the hydrolyzed bottoms mixtures whichboil below 140 C. (10 mm. Hg). This residue is referred to herein astopped. crude, hydrolyzed, isophorone bottoms and is generally similarin structure to the topped, crude, isophorone bottoms described above.

The term isophorone bottoms, as employed herein, is intended to includeall cyclic ketones produced according to the conditions of the foregoingparagraph which contain at least 12 carbon atoms in the molecule,whether topped or untopped, and whether hydrolyzed or unhydrolyzed, andwhich in general have the structural configuration of isophorone or acondensation product thereof. All of said isoohorone bottom compoundsare olefinically unsaturated in their nuc e r portion.

Other cyclic ketones which are olefinically unsaturated in their nucleusand contain 12 or more carbon atoms in the molecule, and which may beused in the present invention, are prepared by the alkaline condensationof mesityl oxide. The latter compound (which may be prepared bycondensing acetone into diacetone alcohol in the presence of soda limeand thereafter subjecting the alcohol to acid-catalyzed dehydration)conden es in the presence of strong (e. g. to 60%) caustic and atelevated temperatures and pressures to form, in the main, C12Cl80,0180260 and higher'molecular ketone units. The desired C12 and higherketones may be obtained from the mesityl oxide condensation product bytopping the same (i. e., distilling off the lower boiling fractions)until a still head temperature of about 95 C. (4 Hg) is reached. Theresidue (bottoms in the still) may then be used as such or it maybestill further topped to a still head. temperature of 160 (4; mm. Hg), at

which point the main portion of the C18 ketones begins to distill.

The polyhalogenated organic reactant may comprise any organic compoundwherein at least 2 and preferably 3 or more halogen atoms are attachedto a single carbon atom. Representative reactants of this variety are,for example, polyhalogenated alkanes such as carbon tetrachloride,chloroform, methylene chloride, carbon tetrabromide, bromoform.methylene bromide, iodoform, methylene chl'oroiodid'e, hexachloroethane,diand trichloroethane, and polyhalogenated fatty acids in. which thehalo radicals are preferably attached in the alpha and/or beta positionwith respect to the carboxyl radical,

as, for example, dichloroacetic acid, triohl'oroacetic acid,alpha,alpha-dichloropropionic acid, alpha,alpha,beta,betatetrachloropropi'onic acid, alpha.alnha-dichlorobutyric acid,alpha,alpha,-

beta-trichlorobutyric' acid, phenyldichloroacetic Hydrogen peroxideBenzoyl peroxide Lauroyl peroxide, Tetraline peroxide Urea peroxideButyryl peroxide Diethyl peroxide Di-tert-butyl peroxide Diacyl peroxideAcetyl benzoyl peroxide Propionyl peroxide Cyclohexanone peroxideAscaridole Alkali and alkaline earth metal'peroxides In carrying out theprocess of this invention, the respective ketonic and halogenatedreactants are combined and admixed with the desired peroxide additive inany suitable type of apparatus, the process being carried out in abatchwise, intermittent or continuous manner. A solvent may or may notbe used, as desired. Equi-molar proportions of the respective reactantsmay be used, and the ketonic reactant may even be present in slightexcess. However, it is preferred that there be from about 1.5 to 5 molesof the polyhalogenated reactant for each mole of ketone present. Theperoxide additive, in turn, should be present in an amount which mayvary from about 0.01 to 0.2 mole per cent. Any elevated temperature maybe used in the execution of the process of this invention, but in orderto provide a comparatively rapid reaction rate and to increase theyield, the temperature is preferably maintained above about C., theconventional practice being to reflux the reaction mixture during thereaction interval. This interval .is subject to considerable variation,and while some reaction takes place after only a few minutes heating,extensive reaction requires use of heating periods of one or more hoursduration. The preferred practice is to reflux the reaction mixture forfrom about 2 to 30 hours, using either atmospheric, subatmospheric' orsuperatmospheric pressures, as desired.

The reaction mixture remaining at the conclusion of the heating intervalcontains the novel halogenated cyclic ketone product and usually someexcess of either one or both reactants. These reaction mixtures arethemselves novel compositions having important uses, they beingemployed, for example, as insecticidal and fungicidal compositions andas lubricant additives. However, it is preferred to remove from thecomposition, as by distillation, washing, or otherwise, any excess ofthe polyhalogenated reactant which may still be present, such removalconsiderably enhancing the utility of the composition as a lubricantadditive. On the other hand, for this as well as other purposes, itappears immaterial that the composition may still contain substantialamounts of the ketone reactant. In many cases it is advantageous toleave this residual ketone in the composition since it here acts as asolvent or partial solvent for the halogenated reaction product per se.These various compositions, which contain excess reactant(s), arenormally dark'in color and vary in viscosity from heavy, thoughpourable, liquids to those of a highly viscous nature. If desired, anyexcess of the ketone" reactant present may also be removed'fromthecomposition, as by distillation (preferably conducted under vacuo) or bythe technique of chromatographic separation. In the latter method, thecomposition is absorbed on a suitable material, as alumina, silica, orthe like, after which it is treated first with a solvent of lowpolarity, as pentane or cyclohexane, to remove the unreacted ketone andthen with a material of higher polarity, as methyl or ethyl alcohol,which in turn removes the halogenated reaction product per se. Theselatter reaction products are dark in color and most are of a solid,resinous character, though some are liquid at room temperature. Allcompositions of this invention, whether freed of halogenated and/orketonic reactants or not, are soluble in ketones, as acetone, methylethyl ketone and diisobutyl ketone; in hydrocarbons, as benzene, xylene,toluene or octane; in ethers, as dioxane, diethyl ether, or di-isopropylether; and in alcohols, particularly higher alcohols such as decanol andthe like. They are insoluble in water. As has been noted above, thesecompositions all form excellent lubricant additives and have a number ofother valuable uses as well.

The following examples illustrate the present invention in various ofits embodiments:

Example I A mixture made up of 310 grams (1 mole) of topped, crude,isophorone bottoms (composed of C16 and higher ketones obtained bytopping bottoms from the isophorone synthesis to a still headtemperature of 140 C. at mm. Hg), 615 grams carbon tetrachloride (4moles) and 9.7 grams of benzoyl peroxide (0.04 mole) is refluxed for 12hours, after which the excess carbon tetra.- chloride is distilled off.The residue is a dark,

highly viscous liquid having a chlorine content of approximately 9.7%and containing approximately 61% of unreacted isophorone bottoms. In twoother similar operations the reflux period is extended in the one caseto 2d he re and in the other to '72 hours. The products obtained fromthe latter two operations, while containing 15.4 and 13.5% chlorine and38 and 4.6% unreacted ketone bottoms, respectively, have essentially thesame physical and chemical properties as does the product prepared usingthe 12 hour reflux period. All these compositions proved capable ofimparting extreme pressure qualities to lubricating oils.

Example II properties are essentially the same as those of the productsdescribed in Example I, and all are excellent lubricant additives.

Example III One mole of the topped, crude, isophorone bottoms materialof Example I is refluxed with 4 moles of dichloroacetic acid in thepresence of 0.05 mole ditertiary-butyl peroxide for a period of 24hours. The resulting reaction mixture is then dissolved in anon-aromatic hydrocarbon solvent having a boiling point range of betweenabout 164' and 233 F., after which the solution is washed with water inorder to remove unreacted dichloroacetic acid. On distilling off thesolvent from the resulting solution, there remains a dark, viscousliquid which contains approximately 12% chlorine. When this process isrepeated using an equivalent amount of trichloroacetic acid in the onecase and of beta,betadichloropropionic acid in the other, in place ofthe dichloroacetic acid reactant, there are obtained products whoseproperties are very similar to those of the material obtained byreacting the isophorone bottoms with the dichloroacetic acid, the chiefdifference being that the material obtained through use oftichloroacetic acid contains a somewhat higher percentage of chlorine(ca. 15%).

Example IV The compositions obtained in the foregoing examples afterremoval of the polyhalogenated reactant, are distilled under vacuo untilstill head temperatures of approximately 200 C. (10 mm. Hg.) arereached. The residues obtained in this manner, which are substantiallyfree of unreacted ketone, solidify on cooling to dark, resinous solidswhich contain from about 20 to 25% chlorine. All are soluble in thevarious hydrocarbon, ketone, alcohol and ether solvents, and areinsoluble in water. Again, all proved to be extremely useful lubricantadditives.

Example V One mole of isophorone is refluxed for 12 hours in thepresence of benzoyl peroxide, in the one case with 4 moles of carbontetrachloride and in the other case with a like amount of chloroform. Inboth cases, after distilling off the excess of polyhalogenated reactant,there are obtained products having a chlorine content of 5.1%. Theseproducts, while dark in color, are somewhat less viscous than are thoseobtained using isophorone bottoms as the starting material.

The various percentages expressed herein are on a Weight basis, unlessotherwise indicated.

The invention claimed is:

1. The method comprising heating, at a temperature above C. for at leastone hour, a reaction mixture comprising (a) a cyclic, olefinicallyunsaturated ketone reactant of the type wherein the carbonyl carbon atomis embraced in the cycle, (b) a reactant selected from the groupconsisting of polyhalogenated alkanes and polyhalogenated fatty acidshaving at least two halogen atoms attached to a single carbon atom, and(c) from about 0.01 to 0.2 mole percent of a peroxide catalyst, saidreactants being employed in the ratio of from about 1 to 5 moles of thepolyhalogenated compound for each mole of the ketone.

2. A composition produced by the method of claim 1.

3. The method comprising heating, at a temperature above 100 C. for atleast one hour, a reaction mixture comprising, (a) isophorone bottoms,(b) a reactant selected from the group consisting of polyhalogenatedalkanes and polyhalogenated fatty acids having at least two halogenatoms attached to a single carbon atom, and (c) from about 0.01 to 0.2mole percent of a peroxide catalyst, the reactants being employed in theratio of from 1 to 5 moles of the polyhalogenated compound for each moleof the isophorone bottoms.

4. The novel composition of matter obtained by heating carbontetrachloride with isophorone at a temperature above 100 C. for at leastone hour in the presence of from 0.01 to 0.2 mole percent of a peroxidecatalyst, said reactants being employed in the ratio of from 1 to 5moles of carbon tetrachloride for each mole of isophorone.

5. The novel composition of matter obtained by heating, at a temperatureabove 100 C. for at least one hour, isophorone bottoms with carbontetrachloride in the presence of from 0.01 to 0.2 mole percent of aperoxide catalyst, said reactants being employed in the ratio of from 71 to 5 moles of carbon tetrachloride for-each mole of isophoi'onebottomsr 6. The novel composition of matter obtained by heating, at atemperature above 100 C'. for at least one hour, isophorone bottoms withchloroform in the presence of from 0.01 to 0.2 mole percent of aperoxide catalyst, said reactants being employed in the ratio of from lto 5- moles of chloroform for each mole of isophorone bottoms.

7. The novel composition of matter obtained by heating, at a temperatureabove 100 C. for at least one hour, isophorone bottoms withtrichloroacetic acid in the presence of from 0.0 1 to 0.2 mole percentof a peroxide catalyst, said reactants being employed in the" ratio offrom 1 to 5 moles of. trichloroaceticacid for each mole of isophoronebottoms.

DAVID E. ADELSON.

Refesences' Cited in the file of this patent UNITED STATES PATENTSNumber Name Date 2,222357 Wblfe NOV. 19, 1940 2,380,009 Arnold'et a1July 10, 1945 2,386,447 Dreisbach Oct. 9, 1945 2,415,796 Li'chty Feb.11, 1947 OTHER REFERENCES Prill, J. Am. Chem, $00., v01. 69 pages 62-63(1947).

1. THE METHOD COMPRISING HEATING, AT A TEMPERATURE ABOVE 100* C. FOR ATLEAST ONE HOUR, A REACTION MIXTURE COMPRISING (A) A CYCLIC, OLEFINICALLYUNSATURATED KETONE REACTANT OF THE TYPE WHEREIN THE CARBONYL CARBON ATOMIS EMBRACED IN THE CYCLE, (B) A REACTANT SELECTED FROM THE GROUPCONSISTING OF POLYHALOGENATED ALKANES AND POLYHALOGENATED FATTY ACIDSHAVING AT LEAST TWO HALOGEN ATOMS ATTACHED TO A SINGLE CARBON ATOM AND(C) FROM ABOUT 0.01 TO 0.2 MOLE PERCENT OF A PEROXIDE CATALYST, SAIDREACTANTS BEING EMPLOYED IN THE RATIO OF FROM ABOUT 1 TO 5 MOLES OF THEPOLYHALOGENATED COMPOUND FOR EACH MOLE OF THE KETONE.